JPH0360326B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a heavy ethynyl compound obtained by polymerization in the presence of a specific catalyst.

Conventionally, aromatic compounds having at least one ethynyl group have been polymerized in the presence of a catalyst consisting of a combination of a titanium halide and an organometallic compound, or a catalyst consisting of a combination of a halide of molybdenum or tungsten and an organotin compound. It is known that an ethynyl compound polymer can be obtained by doing this.

However, these conventional catalysts are easily affected by oxygen, water, etc., and when ethynyl compounds having polar groups containing oxygen, nitrogen, sulfur, amines, nitrile, etc. as substituents are polymerized, the catalysts deteriorate. Polymerization reaction is inhibited.

With this in mind, the present inventors have conducted extensive studies on polymerization catalysts, and have found that the intended purpose can be achieved by using a catalyst consisting of a palladium compound, triorganophosphine, cuprous salt, and organic amine. This discovery led to the completion of the present invention.

That is, the gist of the present invention is characterized in that an aromatic compound having at least one ethynyl group is polymerized in the presence of a catalyst consisting of a palladium compound, triorganophosphine, a cuprous salt, and an organic amine. The present invention relates to a method for producing an ethynyl compound polymer.

To explain the present invention, aromatic compounds having at least one ethynyl group (hereinafter referred to as "ethynyl compounds") include, for example, the general formula (In the formula, R ¹ and R ² represent a hydrogen atom, an ethynyl group, an aryl group that may have an ethynyl group, an aryloxy group, an arylethynyl group, or an aralkyl group.).

Specifically, for example, phenylacetylene, orthodiethynylbenzene, metadiethynylbenzene, paradiethynylbenzene, 1,3,5-triethynylbenzene, 4,4'-diethynylbiphenyl, 4,4'-diethynylbenzene, ethynyl diphenyl ether,
4,4'-diethynyl diphenylacetylene, 4,
4'-diethynyl diphenyl ethylene, biphenyl acetylene, 4-ethynyl diphenyl ether,
4-ethynyldiphenyl acetylene, 4-ethynyldiphenylethylene, 3,5-diethynylbiphenyl, 3,5-diethynyldiphenyl ether, 3,5-diethynyldiphenyl acetylene,
Examples include 3,5-diethynyldiphenylethylene.

The catalyst used in the present invention is a palladium compound,
Consists of triorganophosphine, cuprous salt and organic amine.

Examples of the palladium compound include zero- or divalent organic or inorganic palladium compounds.

Specifically, for example, halides such as palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium acetylacetonate, tetrakistriphenylphosphine palladium, palladium acetate triphenylphosphine, palladium chloride triphenylphosphine. etc. Particularly preferred are palladium chloride, palladium triphenylphosphine, and palladium triphenylphosphine chloride.

As the triorganophosphine, tri-n-
Examples include trialkylphosphines such as butylphosphine and tri-n-hexylphosphine, triarylphosphines such as triphenylphosphine, trimethylphenylphosphine, and triethylphenylphosphine. Particularly preferred are triarylphosphines such as triphenylphosphine.

Cuprous salts include cuprous chloride, cuprous bromide,
Cuprous salts of halides such as cuprous iodide, cuprous salts of aliphatic monocarboxylic acids such as cuprous acetate, cuprous propionate, cuprous oleate, cuprous stearate, etc. Inorganic or organic cuprous salts may be mentioned. Particularly preferred are cuprous chloride and cuprous iodide.

Examples of organic amines include secondary amines such as diethylamine, dipropylamine, methylethylamine, ethylpropylamine, dibutylamine, methylphenylamine, ethylphenylamine, morpholine, methylcyclohexylamine, ethylcyclohexylamine, trimethylamine, triethylamine, Examples include tertiary amines such as tripropylamine, tributylamine, dimethylphenylamine, diethylphenylamine, dimethylcyclohexylamine, diethylcyclohexylamine, and tricyclohexylamine. especially,
Diethylamine, tripropylamine and triethylamine are preferred.

Among these organic amines, liquid ones may be used also as a reaction solvent. In addition, solid substances include aliphatic hydrocarbons such as n-hexane and n-heptane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, benzene, toluene,
It may be used by dissolving it in a solvent such as an aromatic hydrocarbon such as ethylbenzene.

The amount of the above-mentioned components of the catalyst to be used is 0.0001 to 1 mol, preferably 0.0005 to 0.5 mol of the palladium compound, 0.0001 to 1 mol of triorganophosphine, per 1 mol of the ethynyl compound as a reaction monomer.
Preferably 0.0005-0.5 mol, cuprous salt 0.0001
~1 mol, preferably 0.0005 to 0.5 mol, and the organic amine is selected from the range of 0.001 to 20 mol, preferably 0.01 to 10 mol.

Polymerization of the ethynyl compound uses the above catalyst,
In the presence or absence of the above-mentioned solvent, preferably in an inert atmosphere such as nitrogen or argon to prevent the oxidation reaction of triorganophosphine,
150℃, preferably 20-130℃ for 0.1-20 hours,
Preferably, the reaction is carried out for 0.5 to 10 hours.

When a solvent is used, the solvent is ethynyl compound 1
0.5 to 20 moles, preferably 1 to 10 moles
Use in molar range.

The desired polymer of ethynyl compound can be obtained from the reaction solution by conventional separation and purification methods.
That is, when the polymer is produced in a solid state such as a powder, it can be obtained by filtration, followed by washing and drying. In addition, when the polymer is dissolved in the reaction solution, the reaction solution may be concentrated by removing the solvent, or the polymer may be precipitated by injecting it into a poor solvent, followed by washing and drying. It can be obtained by

The ethynyl compound polymer of the present invention thus obtained has good heat resistance and insulation properties, and is useful as a high-temperature insulating material.

Furthermore, when the ethynyl compound polymer of the present invention is doped with a doping agent such as sulfur trioxide, oleum, halosulfonic acid, or sulfur trioxide adduct by a known method, the electrical conductivity can be greatly improved, changing from an insulator to a semiconductor. properties, and can be applied to a wide range of fields such as public electricity conversion materials, battery materials, solid-state displays, optical memories, terminal equipment, and antistatic agents.

EXAMPLES The present invention will be explained in more detail with reference to Examples below.

Example 1 Phenylacetylene 1.08gr (0.01mol),
PdCl ₂ (P(C ₆ H ₅ ) ₃ ) ₂ 0.0331gr, P(C ₆ H ₅ ) ₃ 0.1491
Weigh out 0.0296gr of CuI into a 100ml three-necked flask, and add 30ml of toluene and 20ml of triethylamine.
ml was added, and the mixture was heated under reflux for 3 hours under a nitrogen stream.
The color of the reaction solution changed from brown to pale yellow to red.

After the reaction solution was left at room temperature overnight, the solvent was removed under reduced pressure to obtain 1.0g of a reddish-brown solid.

In the infrared absorption spectrum of this solid, absorption of internal acetylene was observed at 2210 cm ^-1 and absorption of a monosubstituted aromatic compound was observed at 1750 to 1950 cm ^-1 . Also, 2110cm
The absorption of terminal acetylene at 3280 cm ^-1 and 3280 cm ^-1 almost disappeared. After redissolving the reddish-brown solid in toluene,
When methanol was added and reprecipitated, a light brown powder was obtained. The infrared absorption spectrum of this substance was the same as above.

Therefore, it was revealed that the polymerization reaction proceeded due to the reaction of the terminal acetylene.

Example 2 A reaction was carried out in the same manner as in Example 1 except that 1.26 g (0.01 mol) of 1,4-diethynylbenzene was used, and a reddish-brown reaction liquid containing a brown powdery precipitate was obtained. This precipitate was filtered, washed with toluene, and dried under reduced pressure at 60°C to obtain 1.20g of brown powder. This powder did not melt even when heated to 350°C, nor was it soluble in common organic solvents such as toluene, chloroform, and tetrahydrofuran.

The infrared absorption spectrum revealed that the absorption corresponding to the terminal triple bond at 3300 cm ^-1 disappeared.

Example 3 A reaction was carried out in the same manner as in Example 1 except that 1.26 g (0.01 mol) of 1,3-diethynylbenzene was used, and a reddish-brown reaction liquid containing a brown powdery precipitate was obtained. After the same post-processing as in Example 2,
1.10 gr of a reddish-brown solid was obtained. On the other hand, when the reaction was carried out under the same conditions as in this example without adding 20 ml of triethylamine, there was no precipitated product at all after the reaction. The reaction solution was concentrated, and the residue was examined by infrared absorption spectrum, and the result was that the absorption spectrum matched that of 1,3-diethynylbenzene, the raw material.

Therefore, the presence of triethylamine was found to be essential.

Example 4 4,4'-diethynyl diphenyl ether 2.18
When the reaction was carried out in the same manner as in Example 1 except for using gr (0.01 mol), a reaction solution containing a reddish-brown solid was obtained. This solid was washed with toluene and dried under reduced pressure at 60°C to yield 1.8g of brown powder. This powder did not melt when heated to 350°C, nor was it soluble in common organic solvents such as toluene, chloroform, and tetrahydrofuran. The infrared absorption spectrum is the terminal triple bond at 3280 cm ^-1 and 600 to 700
The absorption based on alkynes in cm ^-1 almost disappeared.

On the other hand, PdCl ₂ (P(C ₆ H ₅ ) ₃ ) ₂ , P(C ₆ H ₅ ) ₃ , CuI
The reaction was carried out under the same conditions as in this example, except that . The reaction solution was concentrated, and the residue was examined by infrared absorption spectrum, and the absorption spectrum matched that of the raw material, 4,4'-diethynyl diphenyl ether.

Therefore, PdCl ₂ (P(C ₆ H ₅ ) ₃ ) ₂ , P(C ₆ H ₅ ) ₃ , CuI
It turns out that the existence of is essential.

Example 5 The 1,3-diethynylbenzene polymer obtained in Example 3 and the 4,4'-diethynyl diphenyl ether polymer obtained in Example 4 were mixed in powder form with SO ₃ at room temperature. After treatment with a gas mixture of N ₂ (1:5) for 20 minutes, a black powder was obtained. The infrared absorption spectrum of this black powder has an absorption corresponding to -S-O- at 3400 cm ^-1 , an absorption corresponding to -S-O- at 1200 cm ^-1 , 1400 cm ^-1 , and 580 cm ^-1.
Absorption corresponding to SO ₃ was observed.

Note that SO ₃ was 1.5 and 1.7 per polymer unit, respectively, due to the weight increase. The electrical conductivity of this SO ₃ treated black powder is 3.0×10 ⁻⁴ Ω ⁻¹ cm ⁻¹ and 1.9×
It was 10 ^-4 Ω ^-1 cm ^-1 .

On the other hand, when SO ₃ treatment was not performed, the conductivity was less than 10 ⁻¹⁴ Ω ⁻¹ cm ⁻¹ in both cases.

Claims (1)

[Claims] 1. Ethynyl, which is characterized in that an aromatic compound having at least one ethynyl group is polymerized in the presence of a catalyst consisting of a palladium compound, triorganophosphine, a cuprous salt, and an organic amine. Method for producing compound polymer. 2 The aromatic compound having at least one ethynyl group has the general formula, (In the formula, R ¹ and R ² represent a hydrogen atom, an ethynyl group, an aryl group that may have an ethynyl group, an aryloxy group, an arylethynyl group, or an aralkyl group.) A method for producing an ethynyl compound polymer according to item 1.